When two surfaces are brought in contact with each other, a transfer of electrons may occur resulting in a residual static electrical charge when the surfaces are separated. This phenomena is known as triboelectricity. If the surface is composed of a material that is a conductor, the electrons will dissipate quickly thereby eliminating the excess charge. On the other hand, if the surface is composed of a material that is an insulator (a dielectric), the surface charge takes much longer to dissipate. Thermoplastic polymers are typically excellent insulators and thus are unsatisfactory for uses requiring a nature that will dissipate charges. As the polymers accumulate high charges promoting an attraction for dust and dirt, they can discharge to any lower potential body with which they come in contact. To modify a polymer to have antistatic characteristics and dissipate charges, the conductivity might be increased which in turn causes an increase in the rate of static dissipation. This has been accomplished in the past by the use of antistatic agents to promote static-charge decay of surfaces thereby reducing clinging effect, eliminating spark discharge, and preventing accumulation of dust.
It is well known that static charge can be reduced by increasing the moisture content of the atmosphere, and thus the approach in the past has been to use an antistatic agent which will modify the inherently dielectric polymer to impart hydrophilic properties to it by providing functional groups that attract moisture to it. For instance, it is well known to apply external antistatic agents onto polymers by conventional coating or painting methods. Also, it is well known to employ internal antistatic agents which are volume dispersed by admixing in the polymer; i.e. incorporated into the polymer by compounding or extrusion prior to or during molding or film-forming operations, and which work by migrating to the polymer surface. This migration is colloquially referred to in the art of antistatic polymer technology as a "blooming" or "bleeding" effect. When the antistatic agent has not remained volume dispersed but instead has bloomed or bled to the surface, the mechanism for moisture attraction is the same as with the painted on external antistatic agents. The atmospheric moisture is attracted causing decay or dissipation of static charges, i.e. such films depend on ambient humidity. Accordingly a high rate of blooming is required. Such films can overbloom and lose their antistatic character if subjected to a 24 hour water shower or a prolonged heat exposure.
Many patents show quaternary amines (also referred to as quaternary ammonium compounds or salts) as antistatic agents. Examples are U.S. Pat. No. 3,324,091 to Sauides, U.S. Pat. Nos. 3,445,440, and 3,517,045 both to Susi and Arthen, U.S. Pat. No. 3,894,077 to Horikawa et al, U.S. Pat. No. 4,104,175 to Martinsson et al, U.S. Pat. No. 4,268,583 and T961009 both to Hendy, and U.S. Pat. No. 4,605,684 to Pcolinsky.
Also of interest is Japanese Published Patent Application Kokai No. 59-47243, Ito et al, assignors to Mitsui (published Mar. 16, 1984) which shows an electrically conductive resin composition comprising ethylene/alpha,beta unsaturated carboxylic acid copolymer and a tertiary alkanolamine.
More particularly, U.S. Pat. No. 3,933,779 issued Jan. 20, 1976 to Baron et al assignors to Fine Organics discloses an antistatic polymer blend comprising a synthetic polymer and an antistatically effective amount of a compound of the formula: ##STR1## wherein R is alkyl of 4 to 18 carbon atoms unsubstituted or substituted by halo or aryl.
At pages 18 and 19 of published European Patent Application 0219315 Mott assignor to Dow, date of publication Apr. 22, 1987, is a passage stating that their preferred antistatic material is an acrylate monomer-oligomer mixture containing an alkylether triethyl ammonium sulfate available from Metallized Products under the trade-name Staticure, which material is curable by exposure to an electron beam to a permanent, non-bleeding coating which is not dependent on humidity for its antistatic effect. The passage in EP 0219315 goes on to say that further details concerning this material appear in British Patent Application No. 2,156,362 published Oct. 9, 1985.
British Patent Application No. 2,156,362 is the counterpart of U.S. Pat. No. 4,623,594 issued Nov. 18, 1986 to Keough assignor to Metallized Products. U.S. Pat. No. 4,623,594 claims:
1. An antistatic laminate, both sides of which have antistatic characteristics, comprising: PA1 2. the antistatic laminate of claim 1 wherein said quaternary ammonium compound is a trialkylalkyle-therammonium salt. [Emphasis supplied.] PA1 (A) the polymer containing carboxylic acid moieties is a copolymer of (i) a major amount by mol % of an alpha-olefin of the formula RCH.dbd.CH.sub.2 wherein R is H or C.sub.1 to C.sub.8 alkyl, and (ii) a minor amount by mol % of an alpha,beta-ethylenically unsaturated carboxylic acid, and PA1 (B) the quaternary amine is of the formula EQU [(R.sup.1)(R.sup.2)(R.sup.3)(R.sup.4)N].sup.+ [X].sup.- PA1 wherein PA1 (A) the polymer containing carboxylic acid moieties is a copolymer of (i) a major amount by mol % of an alpha-olefin of the formula RCH.dbd.CH.sub.2 wherein R is H or C.sub.3 to C.sub.8 alkyl, and (ii) a minor amount by mol % of an alpha,beta-ethylenically unsaturated carboxylic acid, and PA1 (B) the quaternary amine is of the formula EQU [(R.sup.1)(R.sup.2)(R.sup.3)(R.sup.4)N]'[X].sup.- PA1 wherein PA1 (1) mixing with heat (A) a polymer containing carboxylic acid moieties and (B) an antistatically effective amount of a quaternary amine wherein: PA1 (A) the polymer containing carboxylic acid moieties is a copolymer of (i) a major amount by mol % of an alpha-olefin of the formula RCH.dbd.CH.sub.2 wherein R is H or C.sub.1 to C.sub.8 alkyl, and (ii) a minor amount by mol % of an alpha,beta-ethylenically unsaturated carboxylic acid, and PA1 (B) the quaternary amine is of the formula EQU [(R.sup.1)(R.sup.2)(R.sup.3)(R.sup.4)N]'[X].sup.- PA1 (2) forming the resultant into a film having one or more layers. PA1 (A) the polymer containing carboxylic acid moieties is a copolymer of (i) a major amount by mol % of an alpha-olefin of the formula RCH.dbd.CH.sub.2 wherein R is H or C.sub.1 to C.sub.8 alkyl, and (ii) a minor amount by mol % of an alpha,beta-ethylenically unsaturated carboxylic acid, and PA1 (B) the quaternary amine is of the formula EQU [(R.sup.1)(R.sup.2)(R.sup.3)(R.sup.4)N].sup.+ [X].sup.- PA1 wherein PA1 (1) a first layer, said layer being an outside layer comprising about 90% or more by weight of ethylene vinyl acetate copolymer and about 10% or less by weight of antiblock, PA1 (2) a second layer, said layer being an interior layer comprising about 65% or more by weight ethylene vinyl acetate copolymer, and about 35% or less by weight of a mixture of (A) a polymer containing carboxylic acid moieties and (B) an antistatically effective amount of a quaternary amine wherein: PA1 (A) the polymer containing carboxylic acid moieties is a copolymer of (i) a major amount by mol % of an alpha-olefin of the formula RCH.dbd.CH.sub.2 wherein R is H or C.sub.1 to C.sub.8 alkyl, and (ii) a minor amount by mol % of an alpha,beta-ethylenically unsaturated carboxylic acid, and PA1 (B) the quaternary amine is of the formula EQU [(R.sup.1)(R.sup.2)(R.sup.3)(R.sup.4)N]'[X].sup.- PA1 wherein PA1 (3) a third layer, said layer being a core layer comprising about 65% or more by weight of a mixture of linear low density polyethylene copolymer and ethylene vinyl acetate copolymer and about 35% or less by weight of a mixture of (A) a polymer containing carboxylic acid moieties and (B) an antistatically effective amount of a quaternary amine wherein: PA1 (A) the polymer containing carboxylic acid moieties is a copolymer of (i) a major amount by mol % of an alpha-olefin of the formula RCH.dbd.CH.sub.2 wherein R is H or C.sub.1 to C.sub.8 alkyl, and (ii) a minor amount by mol % of an alpha,beta-ethylenically unsaturated carboxylic acid, and PA1 (B) the quaternary amine is of the formula EQU [(R.sup.1)(R.sup.2)(R.sup.3)(R.sup.4)N]'[X].sup.- PA1 wherein PA1 (4) a fourth layer, comprising an interior layer the same as layer (2), and PA1 (5) a fifth layer, comprising an outside layer the same as layer (1). PA1 R.sup.1 is selected from H, aryl, or C.sub.1 to C.sub.50 alkyl optionally having one or more non-contigous C.dbd.O or NHC.dbd.O or --S-- or --O-- in the carbon chain, or the same as R.sup.2 ; PA1 each of R.sup.2, R.sup.3, and R.sup.4 is the same or different and selected from H, C.sub.1 to C.sub.18 alkyl optionally substiuted with one or more OH or from --(R.sup.5 --O).sub.a --H where a is an integer from 1 to 10 and R.sup.5 is ethylene or propylene; and PA1 X is an anion selected from chloride, bromide, iodide, fluoride, nitrate, fluoborate, phosphate, C.sub.1 to C.sub.8 alkyl phosphate, sulfate, C.sub.1 to C.sub.8 alkyl sulfate, formate, C.sub.1 to C.sub.8 alkyl or C.sub.6 to C.sub.24 alkaryl or aryl sulfonate, acetate, citrate, propionate, tartrate or carbonate. Preferably, the C.sub.1 to C.sub.8 alkyl phosphate is methyl phosphate or ethyl phosphate, the C.sub.1 to C.sub.8 alkyl sulfate is methyl sulfate or ethyl sulfate, and the C.sub.1 to C.sub.8 alkyl or C.sub.6 to C.sub.24 alkaryl or aryl sulfonate is methanesulfonate, butanesulfonate, benzenesulfonate, or C.sub.1 to C.sub.18 alkyl benzenesulfonate.
(A) a substrate sheet; PA2 (B) a continuous coating on one side of said substrate sheet, said continuous coating comprising the electron radiation cured product of: PA2 R.sup.1 is selected from H, aryl, C.sub.1 to C.sub.50 alkyl optionally having one or more non-contiguous C.dbd.O or NHC.dbd.O or --S-- or --O-- in the carbon chain, or the same as R.sup.2 ; PA2 each of R.sup.2, R.sup.3, and R.sup.4, is the same or different and selected from H, C.sub.1 to C.sub.18 alkyl optionally substituted with one or more OH or from --(R.sup.5 --O).sub.a --H where a is an integer from 1 to 10 and R.sup.5 is ethylene or propylene; and PA2 X is an anion selected from chloride, bromide, iodide, fluoride, nitrate, fluoborate, phosphate, C.sub.1 to C.sub.8 alkyl phosphate, sulfate, C.sub.1 to C.sub.8 alkyl sulfate, formate, C.sub.1 to C.sub.8 alkyl or C.sub.6 to C.sub.24 alkaryl or aryl sulfonate, acetate, trifluoroacetate, citrate, propionate, tartrate or carbonate. The present invention also provides for a film comprising this mixture. PA2 R.sup.1 is selected from H, aryl, or C.sub.1 to C.sub.50 alkyl optionally having one or more non-contiguous C.dbd.O or NHC.dbd.O or --S-- or --O-- in the carbon chain, or the same as R.sup.2 ; PA2 each of R.sup.2, R.sup.3 and R.sup.4 is the same or different and selected from H, C.sub.1 to C.sub.18 alkyl optionally substituted with one or more OH or from --(R.sup.5 --O).sub.a --H where a is an integer from 1 to 10 and R.sup.5 is ethylene or propylene; and PA2 X is an anion selected from chloride, bromide, iodide, fluoride, nitrate, fluoborate, phosphate, C.sub.1 to C.sub.8 alkyl phosphate, sulfate, C.sub.1 to C.sub.8 alkyl sulfate, formate, C.sub.1 to C.sub.8 alkyl or C.sub.6 to C.sub.24 alkaryl or aryl sulfonate, acetate, citrate, trifluoroacetate, propionate, tartrate or carbonate. PA2 R.sup.1 is selected from H, aryl, or C.sub.1 to C.sub.50 alkyl optionally having one or more non-contiguous C.dbd.O or NHC.dbd.O or --S-- or --O-- in the carbon chain, or the same as R.sup.2 ; PA2 each of R.sup.2, R.sup.3, and R.sup.4 is the same or different and selected from H, C.sub.1 to C.sub.18 alkyl optionally substituted with one or more OH or from --(R.sup.5 --O).sub.a --H where a is an integer from 1 to 10 and R.sup.5 is ethylene or propylene; and PA2 X is an anion selected from chloride, bromide, iodide, fluoride, nitrate, fluoborate, phosphate, sulfate, C.sub.1 to C.sub.8 alkyl sulfate, formate, C.sub.1 to C.sub.8 alkyl or C.sub.6 to C.sub.24 alkaryl or aryl sulfonate, acetate, citrate, trifluoroacetate, propionate, tartrate or carbonate; and PA2 R.sup.1 is selected from H, aryl, or C.sub.1 to C.sub.50 alkyl optionally having one or more non-contiguous C.dbd.O or NHC.dbd.O or --S-- or --O-- in the carbon chain, or the same as R.sup.2 ; PA2 each of R.sup.2, R.sup.3, and R.sup.4 is the same or different and selected from H, C.sub.1 to C.sub.18 alkyl optionally substituted with one or more OH or from --(R.sup.5 --O).sub.a --H where a is an integer from 1 to 10 and R.sup.5 is ethylene or propylene; and PA2 X is an anion selected from chloride, bromide, iodide, fluoride, nitrate, fluoborate, phosphate, C.sub.1 to C.sub.8 alkyl phosphate, sulfate, C.sub.1 to C.sub.8 alkyl sulfate, formate, C.sub.1 to C.sub.8 alkyl or C.sub.6 to C.sub.24 alkaryl or aryl sulfonate, acetate, citrate, trifluoroacetate, propionate, tartrate, or carbonate. PA2 R.sup.1 is selected from H, aryl, or C.sub.1 to C.sub.50 alkyl optionally having one or more non-contiguous C.dbd.O or NHC.dbd.O or --S-- or --O-- in the carbon chain, or the same as R.sup.2 ; PA2 each of R.sup.2, R.sup.3, and R.sup.4 is the same or different and selected from H, C.sub.1 to C.sub.18 alkyl optionally substituted with one or more OH or from --(R.sup.5 --O).sub.a --H where a is an integer from 1 to 10 and R.sup.5 is ethylene or propylene; and PA2 X is an anion selected from chloride, bromide, iodide, fluoride, nitrate, fluoborate, phosphate, C.sub.1 to C.sub.8 alkyl phosphate, sulfate, C.sub.1 to C.sub.8 alkyl sulfate, formate, C.sub.1 to C.sub.8 alkyl or C.sub.6 to C.sub.24 alkaryl or aryl sulfonate, acetate, citrate, trifluoroacetate, propionate, tartrate, or carbonate, PA2 R.sup.1 is selected from H, aryl, or C.sub.1 to C.sub.50 alkyl optionally having one or more non-contiguous C.dbd.O or NHC.dbd.O or --S-- or --O-- in the carbon chain, or the same as R.sup.2 ; PA2 each of R.sup.2, R.sup.3, and R.sup.4 is the same or different and selected from H, C.sub.1 to C.sub.18 alkyl optionally substituted with one or more OH or from --(R.sup.5 --O).sub.a --H where a is an integer from 1 to 10 and R.sup.5 is ethylene or propylene; and PA2 X is an anion selected from chloride, bromide, fluoride, iodide, nitrate, fluoborate, phosphate, C.sub.1 to C.sub.8 alkyl phosphate, sulfate, C.sub.1 to C.sub.8 alkyl sulfate, formate, C.sub.1 to C.sub.8 alkyl or C.sub.6 to C.sub.24 alkaryl or aryl sulfonate, acetate, citrate, trifluoroacetate, propionate, tartrate, or carbonate.
(1) an electron beam curable prepolymer; and PA3 (2) an effective amount of a saturated quaternary ammonium compound antistatic agent soluble in said prepolymer the product being a reaction product of the prepolymer and the ammonium compound converted into a substantially solid product.
The laboratory examples of U.S. Pat. No. 4,623,594 show that the particular trialkyl alkylether ammonium salt employed was Emerstat 6660 from Emery Industries. Page 52 of a catalog entitled "Miscellaneous Surfactants" describes Emerstat 6660 as a 100% active liquid cationic compound which offers high performance antistatic capacity, but page 52 does not give any generic chemical formula. It is believed that Emerstat 6660 is a diethoxylated alkyl ammonium salt of the formula (A)(A')N[(CH.sub.2 CH.sub.2 O).sub.n H].sub.2.sup.+ A'0SO.sub.3.sup.- which is further described below.
Of general interest is U.S. Pat. No. 4,678,836 (Jul. 7, 1987) McKinney et al assignors to Dow Chemical. It shows blends of linear low density polyethylene (LLDPE) and ethylene-acrylic acid (EAA).